Betaines



United States Patent 3,360,550 BETAINES Frank M. Cowen, North Plainfield, N.J., and Gloria Bellis, New Rochelle, N.Y., assignors to American Cyanarnid Company, New York, N.Y., a corporation of Maine No Drawing. Original application Dec. 28, 1959, Ser. No. 862,087, now Patent No. 3,225,074, dated Dec. 21, 1965. Divided and this application Sept. 1, 1964, Ser. No. 398,143

3 Claims. (Cl. 260-50113) This application is a division of application Ser. No. 862,087, filed Dec. 28, 1959, now Patent No. 3,225,074, which in turn is a continuation-in-part of application Ser. No. 547,845 filed Nov. 18, 1955, now abandoned.

The present invention relates to new compositions of matter consisting of betaine derivatives, to the processes of preparing them and to their use as germicides.

It has been found that betaine derivatives may be prepared haVing the following structural formula:

wherein R represents long chain aliphatic hydrocarbon radical containing from 10-20 carbon atoms, cycloalkyl, aryl, aralkyl, or alkaryl radicals; M represents a bivalent radical such as -C(=A)D-, B-C(=)- or -B-C(=A)-D in which C is carbon and A, B and D are oxygen, sulfur and imino; R is an alkylene radical (-C I-I containing from 1 to 24 carbon atoms and preferably 1-12 carbon atoms; R and K, may represent R -MR where R selected from the group consisting of R and short chain aliphatic hydrocarbon radicals, i.e. alkyl and alkenyl, hydroxyalkyl, -(C H R' O) H, or -R COOMe, wherein x is a Whole number from 2 to 4, y is a number from 1 to about 100, R is methyl, ethyl, tolyl or phenyl, and Me is hydrogen, ammonium or a metal, particularly an alkali metal or an alkaline earth metal; and R is an alkylene radical (C H containing from 1 to 12 carbon atoms and preferably 1-6 carbon atoms.

Typical specific illustrative examples of R are methyl, ethyl, propyl, isopropyl, butyl sec-butyl, tert-butyl, isobutyl, amyl, tert-amyl, isoamyl, hexyl, heptyl, octyl, nonyl, decyl, hendecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, etc.; allyl butanyl, pentenyl, hexenyl, oleyl, linoleyl, linolenyl, etc.; phenyl, phenethyl, tolyl, xylyl, methyl, xylyl, benzyl, naphthyl, naphthyl methyl, etc.; cyclohexyl, cyclopentyl, etc.

The bivalent radical M, represented by the partial formulas C(=A)D, -B-C(=A)- and B-C(=A)-D- includes, for example, such groupings as arninocarbonyl NHC(=O)--, carbonylarnino -C(=O)-NH, carbonyloxy O(=O)-O; arninocarbonylamino NHC(=O)NH-; the corresponding thio-groupings; and the substituted imino derivatives wherein the 3,360,550 Patented Dec. 26, 1967 the herein after described illustrative examples, it is to be noted that ethylene oxide is the most commonly used oxide but such has been the case primarily for illustrative purposes and is not to be construed as limitative of hydrogen of the imino radical is substituted by alkyl, cy-

cloalkyl, alkenyl, aryl, aralkyl and alkaryl groups.

Representative examples of radicals R and R are met-l1- ylene, ethylene, propylene, butylene, pentamethylene, etc.,

I with the range of carbon atoms being from 1 to 24 and the invention. Consequently, other alkylene oxides such as propylene oxide and isobutylene oxide, as well as styrene oxide may be used.

The radical Me may be hydrogen, ammonium or a metal such as sodium, potassium, magnesium, calcium, etc.

The betaines of the present invention are prepared by initially making intermediate products suitable for conversion to the desired betaines. These intermediate products include, for example, (l) tertiary amines containing amide groupings resulting from the reaction of an acid (including thionic acids) and an aminoalkyl-substituted tertiary amine; (2.) tertiary amines containing amide groupings resulting from the reaction of an acid (including thionic acids) and an aminoalkyl-substituted secondary amine, followed by further treatment of the reaction product with an alkylene oxide; (3) tertiary amines containing ester groupings resulting from the reaction of an acid and an alkan-olamine containing a tertiary amine grouping; (4) tertiary amines containing amide groupings resulting from the condensation of urea and N-substituted ureas with a diamine containing one tertiary amine grouping, etc.

These tertiary amine-intermediate products are then reacted with an omega-halogen-substituted aliphatic acid, such as tx-chloracetic acid, fi-chlorproionic acid, 'y-chlorbutyric acid, etc., in the presence of an alkaline material, such as an alkali metal or alkaline earth metal hydroxide, to form the desired betaine.

The above compounds and radicals have been cited as illustrative of the materials which can be used in the present invention and it is to be pointed out that such is not to be construed as limitative of the invention, but that corresponding and equivalent compounds and radicals may be used within the spirit of the inventive concept.

The invention will be further illustrated in more specific detail by the following examples. It should be understood, however, that although these examples may describe in more particular detail some of the very specific features of the invention, they are given primarily for purposes of illustration and the invention in its broader aspects is not to be construed as limited thereto.

PREPARATION OF INTERMEDIATE AMIDES Example 1 N,NBIS- OLEYLAMID OPROPYL) -N-METHYLAMINE The acid (Acintol fatty acid 1 is a fractionated mixture of tall oil fatty acids and contains about 48% oleic acid, 43% linoleic acid and about 3% saturated acids) and the amine were added along with xylene as an entraining agent to a 3-neck flask fitted with a thermometer, stirrer, water trap and reflux condenser. The mixture was heated at reflux for about seven hours at -195 C. At the end of this period, the theoretical amount of water (1.0 mole) had collected in the water trap. A sample was titrated and found to contain less than 1% uncombined carboxylic acid. It was therefore stripped free of xylene and unreacted amine and used directly for the preparation of the betaine. Yield, 97%

Example 2 N;N-BIS- OLEYIJAMID OPROPYL) -AMINE n at-aaC ONHCHaCHzCEz H CnHai-aa C O NHCHZCHzCHa Reaetants l Mole (s) Gms.

Actinol FA 1 1. 5 Bis-(3-aminopropyD-amine 0. 788 103 By the procedure in Example 1, the mixture was heated for 11 hours at 145-195 C. Stripping gave a 98% yield of product.

Example 3 N,:N-BIS- STEARAMIDOPR OPYL) -N-METHYLAMI'NE cm-u n-aa C aCliacgz OH;

/N Cis-nHsi-aso ONHOHflOHlCH:

Reactants Gms.

Hydrotol 405 l Bis-(3-aminopropyl) -methylamine Hydrofol 405- is a commercial grade of stearic acid and contains about 65% stearic acid, 28% palmitic acid, 2% myristic acid and 6% oleic acid. After heating for" six hours at 152-189 C. and stripping, the product yield was 97%. It set to a hard yellow Wax.

Example 4 N, N-BIS- STEARAMIDOPROPYL) -AMINE Reactants Mole (s) Gms.

Hydrofol 405 1. 3 360 Bis-(3-aminopropyD-amine 0. 683 89 Heating for ten hours at 183185 C. and stripping gave a 100% yield of the amide.

A similar .prepaartion in which nitrogen gas was substituted for xylene gave a quantitative yield after sixteen hours at 138-185 C.

Example 5 V tN,N-BIS- STEARAMIDOISOPROPYL) -AMINE Reactauts Mo1e(s) Gms.

Hydrofol 405 1. 277 Dipropylene triamine. 0. 67

Employing both nitrogen and xylene, a 96% yield was obtained after twenty-two hours at 147-184 C.

Example 6 -N, N-BIS STEARAMIDO ETHYL) -AMINE Reactants I Mole (s) Gms.

Hydrofol 405 1. 0 277 Diethylenetriamiue 0. 5 57 Similar to Example 5 but heated for six hours at 165- 173 C. Yield, 98%.

Example 7 N-LAURAMIDOPRO-PYL-N,-N-DIMETHYLAMINE 5 Reactants M0le(s) I Gms.

Neofat ll l. 5 310 3-dimethylaminopropylamine. 1. 875 191 Similar to Example 5 but benzene substituted for xylene and only 25% of amine added at start. Rest added dropwise over a seven hour period. Total heating time was twenty-eight hours at 113-1645 C. Yield, 98%. (Neofat 11 is a mixture of fatty acids obtained by fractional distillation processes and comprises 90% lauric acid, 9% myristic acid and 1% oleic acid.)

PREPARATION OF INTERMEDIATE ESTERS yield.

Example 9 N,N-BIS- STEAROYLOXYETHYL) -N- (.Z-HYDROXY- Reactants Mole (s) Gms.

Hydrotol 405 Trlethanolamine Heating for eleven hours at 141-190 C. by previous methods gave a tan wax, 96% yield.

Example 10 N,N-BIS- STEAK OYLOXYETHYL) -N-METHYLAMINE Reactants Mole (s) l Gms.

Hydrofol 405 1. 0 277 Diethanolrnethylamlne 0. 5 61 Thirteen hours at 135l60 C. gave a 100% yield of the ester.

PREPARATION OF INTERMEDIATE TERTIARY AMINES (HYDROXYETHYLATION) Example 11 N,-N-BIS- OLEYLAMIDOPROPYL) -HYDROXYETHYL- 6 5 AMINE C HaaC ONHCHzCHzCEz CHgCHzOH /N CnHazC ONHCHaCHzCH:

Reactants Equivalents Grns.

N,N-bis-(oleylamidopropyl)-amine (Ex. 2) 281 Ethylene oxide 19 The amide was dissolved in 300 g. of isopropyl alcohol and treated with the ethylene oxide for 1.6 hours at 7881.5 C. Stripping gave the hydroxyethylated product in quantitative yield.

Example 12 N,N-BIS- STEARAMIDOPROPYL) -HYDROXYETHYL- AMINE Reactants Equivalents Grns.

N,N-bis-(stearamidopropyl)amine (Ex. 4). 0. 65 421 Ethylene oxide 29 Isopropyl alcohol 420 As Example 11 except the mixture was treated for two hours at 73-82 C.

Treated for 2.3 hours at 5090 C. Quantitative yield of hydroxyethylated product.

Example 14 N,N-BIS- STEARAMIDOETHYL) -HYDR OXYETHYL- AMINE Reaetauts Equivalents Gms.

N,N-bis-(stearamidoethyl)-amine (Ex. 6)- 0. 298 Ethylene oxide 23. 5 Isopropyl alcohol 237 Treated for 2.8 hours at 6780 C. Quantitative yield.

PREPARATION OF BETAINES Example 15 N,N-BIS- OLEYLAMIDOPROPYL) N-METHYL-N-CAR- BOXYMETHYLAMMONIUM BETAINE 17 330 ONHCHnCHgCE? OH;

Gms.

React-ants Equivalents N,N-bis(oleylamidopropyl)-N-methylamine (Ex. 1)

The chloracetic acid was suspended in the water in a flask of suitable size equipped with a stirrer, thermometer, and reflux condenser. The acid was neutralized with the sodium hydroxide as a 40-50% aqueous solution while cooled in an ice bath. The amine in alcohol was added and the mixture refluxed for five hours.

At the end of the reaction the mixture was diluted with alcohol and evaporated to dryness. The resulting solid was dissolved in benzene and the insoluble salt (sodium chloride) removed by filtration. The filtrate was evaporated to dryness to give a brown paste in quantitative yield.

The product was useful as a germicide and killed 24- hour cultures of Salmonella typhosa in minutes at 20 C. in dilutions up to 1:1000.

It was also useful as a softening agent for textiles, par- 5 ticularly cottons.

It is to be noted that the P MR grouping in Example is, in effect, an alkenylarnidoalkyl radical, as compared to an alkylamidoalkyl radical (Example 17), an alkyloxyalkyl radical (Example 21), an alkylcarbarnylalkyl radical (Example 23), an alkarylamidoalkyl radical (Example 31), a cycloalkylamidoalkyl radical (Example 33) or the thio-substituted alkylcarbamylaminoalkyl, alkylamidoalkyl and arylamidoalkyl radicals (Examples 34, 35, 36).

Example 16 N,'N-BIS-(OLEYLAMIDOPROPYL) N, N BIS('CARBOXY- METHYLAMMONIUM) BETAINE, MONOSODIUM SALT g C17H33C0NHCH2CH2G CH;COO-.Na+

Reaetants Equivalents Gms.

N,N-bis-(oleylamidopropyl)-amine (Ex. 2)- 0. 25 176.

Chloracetic acid 0.50

Sodium hydroxidm... 0. 75

Reflux for six hours and workup gave a quantitative yield of viscous brown liquid.

Example 17 A reflux time of five hours and usual work up gave a yellow wax (quantitative).

The product was useful as a cotton softener. It was also useful as a germicide and killed 24-hour cultures of Salmonella typhosa in 10 minutes at 20 C. in dilutions up to 1:1000.

Example 18 N- STEAR'AMIDOPROPYL) -N, N-DIMETHYL N-CARBOXY- METHYLAMMONIUM BETAI'NE C17H35OONHCH1CH1CH9 CH3 CH3 CHQC O O- Rcactants Equivalents Gms.

N-(stearamidopropyl)-N,N-dimethyl- 0. 50 201.

amine.

Chloracetic acid 0. 50

Sodium hydroxide. 0. 50

Ethan 150 ml Water Five hours refluxing and Workup gave a quantitative yield of a white wax. The product was useful as a deter- 7 gent and as an anti-static agent.

7 Example 19 NJN BIS (OLEYLAMIDOPROPYL) 'N (2 HYDROXY- ETHYL)N-CARBOXYMETHYL AMMONIUM BETAINE CnHaaCONHCHzCHzOHz CH2CH2OH 01 E ONHCHzCHzCH: CHzC O 0- Reactants Equivalents Gms.

N,N-bis-(oleylamidopropyl)-N-(2- 0.20 300 (including isohydroxyethyD-amine (Ex. 11).

Chloraeetic acid O. 20 Sodium hydroxide 0. 20 Isopropyl alcohoL. Water propyl alcohol).

30 ml.+ 40 ml.

Refluxing for five and three-quarter hours and recovery gave a viscous sticky brown paste in quantitative yield.

Example 20 N,N BIS (S-TEARAMIDOPROPYL) "N (2 HYDROXY- ETHYL)N-CARBOXYMETHYL AMMONIUM BETAINE 017E350 ONHCHZCHZCEZ CHZCHZOH Reactants I Equivalents Gms.

N,N-bis-(stearamidopropyD-N-(Z- 0. 65

hydroxyethyD-amine (Ex. 12).

Chloracetic acid 0. 65 1 Sodium hydroxide. 0. 65

Isopropyl aleohoL..-

Water .I

870 (including isopropyl alcohol).

A quantitative yield of tan or brown wax was obtained after about six hours of reflux and recovery.

Example 21 1N*STEAROYLOXYETHXLN,NBIS- 2-HYDROXYETHYL) .N-CARBOXYMETHYL AMMONIUM IBETAI NE The refluxing time was six and three-quarter hours. Quantitative yield of tan wax. The product was useful as a detergent and anti-static agent.

Example 22 N,'N BIS (STEAROYLOXYETHYL) N (2 HYDROXY- ETHYL) -N-CARBOXYMETHY'L AMMONIUM BETAINE (31711 0 0 O CHzCHz CHaCHgCH (11711350 0 O CHaCfis CHgC O O- Reaetants Equivalents l Gms.

N,N-bis-(stearoyloxyethyl)-N-(2-hydroxy- 0.086 200.

ethyD-amine (Ex. 9). Chloroaeetic acid 0. 086

Six and three-quarter hours reflux gave a 92% yield of tan wax.

8 Example 23 MN-BIS N OCTADECYLCARBAMYLETHYL)-N-(2HY- DROXYETHYL) N CARB'OXYMETHYL AMMONI'UM BETAINE lB 31 HO O CHzC a CHaCH OH CmHmNHCOCHgCH; CH1COO" 1O Reaetants Equivalents Gms.

N,N-bis-(N-0ctadecylcarbamylethyD-N- 0.071 72.

(2-hydroxyethyl) -an1ine. Chloroacetic acid A refluxing time of seven hours resulted in the recovery of a quantitative yield of a brown wax. It possessed utility as a textile softener.

Example 24 N, N-BIS(STEARAMIDOISOPROPYL) N (2 HYDR-OXY- ETHYL)--N-CARBOXYMETHYL AMMONIUM BETAINE Ci7H35C ONHCHBCE C17H C ONHCHa-CH CHQCHZOH Reactants Equivalents I Gnis.

N ,N-bis- (stearamidoisopropyD-N- (2-hydroxyethyD-amine. Chloroacetic acid 0. 50

0. 50 560 (including isopropylalcohol) Seven hours refluxing gave an orange-brown paste. Recovery was quantitative.

Example 25 &N,-N-BIS- (STEARAMIDOETHYL) -N- (2-HYDROXYETHYL) N-CARBOXYMETHYL AMMONIUM BETAI NE C1 H CONHCH2CH2 CHzCHzOH 01 E 0 ONHCHnCHz CHzOO O- Reactants Equivalents Gms.

N,N-bis-(steararnidoethyl)-N-(2- hydroxyethyD-amine. Chloroacetie acid 0. 493 555 (including isopropyl alcohol).

A reflux time of five hours and Workup gave a quantitati've yield of a tan wax.

Example 26 N,N-BIS- STEAROYLOXYETHYL) ET-METHYL-N-CAR- BOXYMETHYLAMMONIUM BETAINE Reactants Equivalents N,N -bis-(stearoyloxyethyl)-N-methy1amine.

9 10 Seven and one-quarter hours was sufficient reflux time The procedures set forth in Example 1 were followed to give a 94% recovery of a tan wax product. It was usesubstantially as set forth therein. The yield was quantiful as a cotton softener. tative.

Example 27 N, N-BIS(PROPYLAMIDOPROPYL)-N-METHYL-iN-CAR- ET A M NI K ETAI. D N-(LAURAMIDOPROPYL)-N,N-DIMETHYL-N=CARBOXY- BOXYM HYL M 0 UM B METHYIJAMMONIUM BETAINE CQH1CONH0H2OHC1 /CH:

+ C11H23CONHCH2CH2CH2 CH3 N CaH1C0NHCHzCH2CH1 omooo- 0E3 \OH2COO The procedures of Example were followed, using substantially equal molal amounts of amine, chloracetic acid and sodium hydroxide. The yield was quantitative.

Reactants Equivalents Gms.

Example 31 N-(lauramidopropyl) -N,N-dimethylal. 57 426.

mine. 15 N,'N-BIS (DODECYLBENZYLAMIDOPROPYL) -N- Chloroacetie acid 1. 73 DECYLAMINE Sodium hydroxide" 1. 73 5132331 3111:::::: 1311;113:3333: 553 El: CIHMGBEC 51 fi Heated at reflux for nine and one-half hours; gave CizHzsctHrCoNHCHzcHaca quantitative yield of soft tan Wax.

Example 28 Reactants 01 (s) Gms.

ENE GLYCOL PRODUCT ppodecylbenzoic acid H 1 293 11E350 NHCHzCHzCEg /oHZoH o oH, H, p py ecy mme 0.525 184 Procedures as in Example 1.

WHBSC ONHCHNHNH OHQG O O N,N-BIS (DODECYLBENZY'LAMIDOPROPYL) JN-DECYEN- CARBOXYETHYL AMMONIUM BETAIN'E Reactants Equivalents Gms.

30 0111125051140 oNHomomoH. 0.011,. Betaine in Ex. 19. 0.1 as Ethylene oxide *0. 26 p py elwhoL 111 CHH25C5H4C oNHcmomoH, omomo o 0- Using chlorpropionic acid and sodium hydroxide, as Actually reacted. Excess used. Example 15.

The betaine was dissolved in the alcohol, the mixture heated to 20 C. and ethylene oxide added at 6278 C. for 2 /3 hours. The final product, a polyethenoxy derivative obtained in quantitative yield, was a brown 47% solution.

This material contained 2.6 mols of combined ethylene oxide for each mol of the original betaine. It was therefore a mixture of two or more ethylene oxide condensation products.

Example 32 N,N-BIS CYCLOHEXYLAMIDOPROPYL) -N-O CTYL-N- 'CARB OXYMETHYL AMMONIUM BE'IAINE Using cyclohexyl carboxylic acid and his-( 3-aminopropyD-octylamine to form the intermediate tertiary aple 29 mine and chloracetic acid and sodium hydroxideto form POLYETHYLENE :G'LYCOL PRODUCT the betaine. C11H CONHCHzCHzGHz cmomowmomomn Example 33 01111350 oNnomcmofiz omoo o- CHHHNHCONHCH5CHQCH2NLCHCO0" Reactants Equivalents Gms.

Using N-dodecylurea and S-ammopropyldrmethyl- Betaine in Ex. 19 M 88 amine in the formation of the tertiary amine, followed by Ethylene oxide... *3.0 1ts reaction with chloracetic ac1d and sodium hydroxide ISOPwPYl 111 in the formation of the betaine.

Example 34 Actually reacted. Excess used.

The betaine was dissolved in the alcohol, the mixture :11 heated to 20 C. (under 100 p.s.i.) and ethylene oxide H NHOSNH added at 62-78 C. for 7 hours. The final product, a 25 OH2GH2CH2N+ 0112000 polyethenoxy derivative, was obtained in substantially a H8 quantitative yield. It was useful as an emulsifier.

Example 30 N,N-BIS(PROPYLAMIDOPROPYL)-N-METHYLAMINE C3H7CONHOH2CH2GH2 CH3 Using N-do-decyl thio-urea and 3-aminopropyldimethylamine in the formation of the tertiary amine, followed 65 by its reaction with chloracetic acid and sodium hydroxide in the formation of the betaine.

N Example 35 051170 oNHornomom M 0 1100ONH(CH2)izN+CHzOOO- Beactants I M0le(s) Gms. H:

propionic acid 1 74 Using butyric acid and dimethylaminolaurylamine to Bis-(3-aminopropyl)-methyla.mine 0.525 76 form the tertiary amine and chloracetic acid and sodium 7 hydroxide to form the betaine.

Exan tp le 36 Using ethanethionic acid and a slight excess of 3-dimethylaminopropylamine in the formation of the intermediate tertiary amine and chloropropionic acid and sodium hydroxide in the formation of the betaine.

Example 3 7 H 0211; COH5C-NHCH2CHZCHIN+CH2CH2CH2000- Using thiobenzoic acid and a slight excess of S-diethylaminopropylamine in the formation of the intermediate tertiary amine and chlorobutyric acid in the formation of the betaine.

The products of the present invention were determined to be useful as germicides. One specific evaluation of a particular product is set forth below as illustrative of such utility. The product was N-(lauramidopropyl)-N,N- dimethyl-N-carboxymethylammonium betaine (Example 27) used on a 35% solids basis and the test procedure used was the RDA. method described in Circular #198, United States Department of Agriculture. The test organism was a 24-hour culture of Salmonella Iyphasa (Hopkins) and the incubation period was 48 hours at 37 C. The following table indicates the results obtained.

TABLE 1 Evidence of Growth After- 5 mins. mine. I mins.

Legend:

+ indicates growth.

indicates no growth.

Asa control and comparison, a similar test procedure was used on a 35% solids solution of stearamidopropyldimethyl-B-hydroxyammonium dihydrogen phosphate (SP). This product (SP) is not a product of the present invention but was selected as it bears some structural resemblance to the products of the present invention. The following table indicates the results obtained.

Legend:

+ indicates growth. indicates no growth.

The above tables indicate that a 1:1500 dilution of the betaine killed a 24-hour culture of Salmonella typhcsa in 10 minutes at a temperature of 20 C. This corresponds to a 1:85 dilution of phenol. The phenol coeflicient is therefore 18.1. With regard to product SP, the 24-hour culture of Salmonella typhora Was killed in 10 minutes at 20 C. with a dilution of 1:25. This corresponds to a 1:85 dilution of phenol. The phenol coeflicient is therefore 0.3.

Although we have described specific examples of our inventive concept, we consider the broad aspects of the same not to be limited to the specific substances menti-oned therein but to include various other compounds of equivalent function and constitution as set forth in the claims appended hereto. It is understood that any suitable changes, modifications and variations may be made without departing from the spirit and scope of the invention.

What is claimed is:

1. Betaines having the formula where R is an aliphatic hydrocarbon radical of from 10 to 20 carbon atoms selected from the group consisting of long chain saturated aliphatic and long chain alkenyl aliphatic radicals, R and R are alkylene radicals of from 1 to 12 carbon atoms, R, is a member of the group consisting of C H in which n is a Whole number from 1 to 10 and C H .-OH in which n is a whole number from 1 to 10 and (C H.;,.O) H in which x is a whole number from 2 to about 100 and R is a member of the group consisting of R --R ,--COOH and R COOMe in which R R R and R are as defined above and Me is a monovalent saltforming radical, and X is selected from the group consisting of O and S.

2. Betaines having the formula where R is a long chain saturated aliphatic hydrocarbon radical of from 10 to 20 carbon "atoms, R and R are short chain alkylene radicals, R is a member of the group consisting of C H- +1 in which n is a whole number from 1 to 10 and -C H .O H in which n is a whole number from 1 to 10 and (C H .OH) *H in which x is a whole number from 2 to about 100 and R is a member of the group consisting of R 0 RrNH-ii-Rr- -R COOH and R COOMe in which R R R and R are as defined above and Me is a monovalent saltforming radical.

3. N,N bis (N' octadecylcarbarnylethyl) N (2- hydroxyethyl)-N-carboxymethyl ammonium betaine.

References Cited UNITED STATES PATENTS 2,777,872 1/1957 Sclracklett 260501 2,935,493 5/1960 Sohuller et a1. 260-501 LORRAINE A. WEINBERGER, Primary Examiner.

CHARLES B. PARKER, Examiner.

A. H. SUTTO, M. B. WEBSTER, Assistant Examiners. 

1. BETAINES HAVING THE FORMULA 